CN101709516A - Method for preparing toughening agent modified phenolic fiber - Google Patents
Method for preparing toughening agent modified phenolic fiber Download PDFInfo
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- CN101709516A CN101709516A CN200910219172A CN200910219172A CN101709516A CN 101709516 A CN101709516 A CN 101709516A CN 200910219172 A CN200910219172 A CN 200910219172A CN 200910219172 A CN200910219172 A CN 200910219172A CN 101709516 A CN101709516 A CN 101709516A
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Abstract
The invention discloses a method for preparing a toughening agent modified phenolic fiber, which consists of the steps of material mixing, reflux reaction, vacuum drying, preparation of nascent fiber, preparation of a curing liquid, curing reaction, washing and drying, and performance index test. The toughening agent is added to prepare a precursor raw material during preparing a thermoplastic phenolic resin; the toughening agent modified phenolic fiber is obtained through melt spinning and curing; compared with the conventional method for preparing resin fiber, the preparation method is simple and convenient; and the prepared toughening agent modified phenolic fiber has high strength and good toughness, improves heat resistance, and has excellent knitting property.
Description
Technical field
The invention belongs to high molecular functional fibrous material technical field, be specifically related to improve the phenolic fibre mechanical property and keep its excellent heat resistance can method.
Background technology
Phenolic fibre has good fire-retardant and heat resistance, the flame resistant material that can be used for making rocket nozzle, flameproof enclosure, thermal insulation board, high temperature dust bag, work at flame or high temperature.Can be used for the heat insulator of resistance to chemical attack in the chemical industry equipment, the heat preserving exterior wall of building etc. simultaneously.The anti-solvent that phenolic fibre is good, antiacid performance make it be suitable for doing filtering material, and the chemical products under the higher temperature are filtered and screened.Phenolic fibre Nomex and paper can be used for friction material, conductive material, padded coaming etc., for example big battery terminal, high quality speaker buffer etc.
But some structural defectives of phenolic fibre have a strong impact on its use.The easy oxidation of phenolic hydroxyl group and methylene, heat resistance, oxidative resistance are affected; Especially phenolic fibre belongs to the non-crystalline type fiber because of only being linked to each other by methylene between phenyl ring, so intensity is low, wears no resistance.For improving the performance of phenolic fibre, enlarge its scope of application, some scholars study it.Ohtomo etc. (US Patent 3996327) adopt polyamide, poly benzoate and polyethylene terephthalic acid (TPA) that novolac resin is modified, goods not only have good weaving property, excellent stretching and rebound performance do not influence its heat-proof combustion-resistant performance simultaneously again.Okuhashi etc. (US Patent3808289) mix phenolic resin as matrix resin with phosphide and polyamide-based material, improve the firing resistance of goods, and should the dyeing and bleachability of fiber.More than all be by the simple physics blend to STUDY ON THE MODIFICATION OF PENOLIC RESIN, modifier is introduced in the structure of phenolic resins because the compatibility of modifier and phenolic resins is relatively poor, thereby influence the performance of phenolic fibre.
Summary of the invention
Technical problem to be solved by this invention is to overcome above-mentioned phenolic fibre preparation method's shortcoming, providing a kind of is precursor with the high molecular high-ortho novolac resin, and introduce flexible fatty backbone by chemical bonding, make goods have good toughness and intensity, keep the preparation method of the toughening agent modified phenolic fiber of its excellent heat resistance energy simultaneously.
Solving the problems of the technologies described above the technical scheme that is adopted is that it comprises the steps:
1, batching
Take by weighing phenolic compound, aldehyde compound, organic acid or inorganic acid, divalence acetate, flexibilizer, place reactor, stir, the mol ratio of phenolic compound and aldehyde compound, organic acid or inorganic acid, divalence acetate is 1: 0.50～0.90: 0.005～0.025: 0.005～0.020, and the mass ratio of phenolic compound and flexibilizer is 1: 0.01～0.07.
Above-mentioned phenolic compound is phenol or m-cresol; Aldehyde compound be formaldehyde or acetaldehyde or with the paraformaldehyde of quality such as formaldehyde, paraformaldehyde is that the degree of polymerization is 8～100 low molecular weight polyformaldehyde, is produced by the rich Dihua worker Co., Ltd in Tianjin; Divalence acetate is manganese acetate or cobalt acetate or Schweinfurt green, and divalence acetate is first catalyst in course of reaction; Organic acid is maleic acid or citric acid or acetic acid, and inorganic acid is a hydrochloric acid, and organic acid or inorganic acid are second catalyst in chemical reaction process; Flexibilizer is that molecular weight is that 4000～200000 polyethylene glycol, ternary nylon, molecular weight are any one in 48000 the polyvinyl chloride.
2, back flow reaction
Reactant is heated to 95～102 ℃ under stirring, reacted 1～9 hour.
3, vacuumize
After reaction finishes, product is put into the vacuum drying oven of vacuum for-0.07MPa, continue to be heated with stirring to 180 ℃, vacuumize 4 hours is prepared into toughening agent modified novolac resin.
Prepared toughening agent modified novolac resin adopts the softening point of full-automatic bituminous softening-point test device by the toughening agent modified novolac resin of GB/T8146-2003 " rosin experimental technique " test; By GB/T14074.13-93 " wood adhesive and resin detection method free-phenol content assaying method thereof " toughening agent modified thermoplasticity is expected that urea formaldehyde carries out the free phenol assay; Adopt gel permeation chromatography, measure toughening agent modified novolac resin molecular weight and distribution thereof down at 35 ℃, splitter is that (HR 1.0 for Aquapak A-440, HR 2.0, HR 3.0), the flow rate of solvents tetrahydrofurane is 1.0mL/ minute, and standard specimen is that molecular weight is the monodisperse polystyrene of 474～205000g/mol; Adopt the DEPT-135 spectrum, calculate phenolic resins peak (30ppm) the area S of neighbour-neighbour's link
1, adjacent-to phenolic resins peak (35ppm) the area S of link
2With right-to the link novolac resin peak (40ppm) area S
3, calculate resin neighbour-contraposition ratio by following formula:
4, preparation as-spun fibre
Toughening agent modified novolac resin is put into the melt spinning device spinning, the concrete grammar of melt spinning is the preparation method that 3650102 the disclosed fiber of United States Patent (USP) forms from the direct drawing-off of molten according to the patent No., being about to the toughening agent modified novolac resin of 100g packs in the melt spinning still of single hole spinnerets with 1.9mm aperture, be warming up to 135 ℃, toughening agent modified novolac resin becomes molten, melt flows out from spinneret orifice, the drawing-off top roll, drafting rate is 915m/ minute, is prepared into as-spun fibre.
5, preparation consolidation liquid
Water intaking, acid, aldehyde compound are mixed with consolidation liquid, and water is 1: 0.1: 0.2 with the mol ratio of acid, aldehyde compound.
Above-mentioned aldehyde compound be formaldehyde or acetaldehyde or with the paraformaldehyde of quality such as formaldehyde; Above-mentioned acid is hydrochloric acid or sulfuric acid or oxalic acid or phosphoric acid, promptly uses 1 mole hydrochloride or 1/2 mol sulfuric acid or 1/2 mole of oxalic acid or 1/3 mole of phosphoric acid.
6, curing reaction
As-spun fibre is placed consolidation liquid, and the quality of as-spun fibre is 2% of a consolidation liquid gross mass, at the uniform velocity is warming up to 100 ℃ in 6 hours, isothermal reaction 2.5 hours.
7, washing is dry
After reaction finishes, take out fiber, use deionized water rinsing 3～5 times, dry naturally, be prepared into toughening agent modified phenolic fiber.
8, testing performance index
TENSILE STRENGTH, elastic modelling quantity, limited oxygen index to prepared toughening agent modified phenolic fiber are tested.
In batching step 1 of the present invention, the preferred molar ratio of phenolic compound and aldehyde compound, organic acid or inorganic acid, divalence acetate is 1: 0.65～0.90: 0.009～0.020: 0.005～0.015, and phenolic compound is 1: 0.04～0.06 with the preferred mass ratio of flexibilizer.In back flow reaction step 2, reactant preferably is heated to 95～102 ℃, reacted 2～7 hours under stirring.
In batching step 1 of the present invention, the optimum mole ratio of phenolic compound and aldehyde compound, organic acid or inorganic acid, divalence acetate is 1: 0.70: 0.010: 0.007, and the optimum quality ratio of phenolic compound and flexibilizer is 1: 0.05.In back flow reaction step 2, reactant is heated to 95～102 ℃ under stirring, optimum response 5 hours.
In batching step 1 of the present invention, preferred Schweinfurt green of divalence acetate or cobalt acetate, preferred maleic acid of organic acid or inorganic acid or hydrochloric acid, the flexibilizer preferred molecular weight is that 10000 polyethylene glycol or molecular weight are 200000 polyethylene glycol or ternary nylon.
In batching step 1 of the present invention, divalence acetate optimal selection Schweinfurt green, organic acid optimal selection maleic acid, flexibilizer optimal selection ternary nylon.
The present invention adds flexibilizer and is prepared into precursor material when the preparation novolac resin, through melt spinning and curing, be prepared into toughening agent modified phenolic fiber, compare with existing resin fibre preparation method, the preparation method is easy, prepared toughening agent modified phenolic fiber intensity height, good toughness, heat resistance improve, and have good knitting property.
The specific embodiment
The present invention is described in more detail below in conjunction with embodiment, but the invention is not restricted to these embodiment.
Embodiment 1
With 1 mole of phenol is that example is prepared into toughening agent modified phenolic fiber, and used other raw materials and preparation method comprise the steps:
1, batching
Get phenol 94g, paraformaldehyde 22.10g, maleic acid 1.16g, Schweinfurt green 1.40g, ternary nylon 4.70g, place reactor, stir, the mol ratio of phenol and paraformaldehyde, maleic acid, Schweinfurt green is 1: 0.70: 0.010: 0.007, the mass ratio of phenol and ternary nylon is 1: 0.05, and paraformaldehyde is that the degree of polymerization is 8～100 low molecular weight polyformaldehyde.
2, back flow reaction
Reactant is heated to 95～102 ℃ under stirring, isothermal reaction 5 hours.
3, vacuumize
After reaction finishes, product is put into the vacuum drying oven of vacuum for-0.07MPa, continue to be heated with stirring to 180 ℃, vacuumize 4 hours is prepared into toughening agent modified novolac resin.
Prepared toughening agent modified novolac resin adopts the softening point of full-automatic bituminous softening-point test device by GB/T8146-2003 " rosin experimental technique " test novolac resin, and the softening point of surveying is 132 ℃; By GB/T 14074.13-93 " wood adhesive and resin detection method free-phenol content assaying method thereof " novolac resin is carried out the free phenol assay, the free phenol content of surveying is 1.3%; Adopt gel permeation chromatography, measure phenolic resins molecular weight and distribution thereof down at 35 ℃, splitter is that (HR 1.0 for Aquapak A-440, HR2.0, HR 3.0), the flow rate of solvents tetrahydrofurane is 1.0mL/ minute, and standard specimen is that molecular weight is the monodisperse polystyrene of 474～205000g/mol, and the molecular weight Mw that measures novolac resin is 11632; Adopt the DEPT-135 spectrum, calculate phenolic resins peak (30ppm) the area S of neighbour-neighbour's link
1, adjacent-to phenolic resins peak (35ppm) the area S of link
2With right-to the link novolac resin peak (40ppm) area S
3, calculate resin neighbour-contraposition ratio by following formula (1):
Adjacency pair position ratio is 3.0 phenolic resins.
4, preparation as-spun fibre
Toughening agent modified novolac resin is put into the melt spinning device spinning, the concrete grammar of melt spinning is the preparation method that 3650102 the disclosed fiber of United States Patent (USP) forms from the direct drawing-off of molten according to the patent No., being about to the toughening agent modified novolac resin of 100g packs in the melt spinning still of single hole spinnerets with 1.9mm aperture, be warming up to 135 ℃, toughening agent modified novolac resin becomes molten, melt flows out from spinneret orifice, the drawing-off top roll, drafting rate is 915m/ minute, is prepared into as-spun fibre.
5, preparation consolidation liquid
Water intaking 90g, mass concentration are that 36% hydrochloric acid 50.70g, mass concentration are 37% formaldehyde 81.10g, are mixed with consolidation liquid according to a conventional method, and the mol ratio of water and hydrochloric acid, formaldehyde is 1: 0.1: 0.2.
6, curing reaction
Get as-spun fibre 2g and put into the 100g consolidation liquid, average rate was warming up to 100 ℃ in 6 hours, isothermal reaction 2.5 hours.
7, washing is dry
After reaction finishes, take out fiber, use deionized water rinsing 3～5 times, dry naturally, be prepared into toughening agent modified phenolic fiber.
8, testing performance index
TENSILE STRENGTH, elastic modelling quantity, limited oxygen index to prepared toughening agent modified phenolic fiber are tested, and test result sees Table 8.
Embodiment 2
With 1 mole of phenol is that example is prepared into toughening agent modified phenolic fiber, and used other raw materials and preparation method comprise the steps:
In batching step 1; get phenol 94g, paraformaldehyde 15.78g, maleic acid 0.58g, Schweinfurt green 1.00g, ternary nylon-20 .94g; place reactor; stir; the mol ratio of phenol and paraformaldehyde, maleic acid, Schweinfurt green is 1: 0.50: 0.005: 0.005, the mass ratio of phenol and ternary nylon is 1: 0.01.Other steps are identical with embodiment 1.
Embodiment 3
With 1 mole of phenol is that example is prepared into toughening agent modified phenolic fiber, and used other raw materials and preparation method comprise the steps:
In batching step 1; get phenol 94g, paraformaldehyde 28.42g, maleic acid 2.90g, Schweinfurt green 4.00g, ternary nylon 6.58g; place reactor; stir; the mol ratio of phenol and paraformaldehyde, maleic acid, Schweinfurt green is 1: 0.90: 0.025: 0.020, the mass ratio of phenol and ternary nylon is 1: 0.07.Other steps are identical with embodiment 1.
Embodiment 4
In above embodiment 1～3 batching step 1, raw materials used phenol is replaced with equimolar m-cresol, maleic acid is replaced with equimolar citric acid or acetic acid or hydrochloric acid, Schweinfurt green is replaced with equimolar manganese acetate or cobalt acetate, paraformaldehyde such as uses to replace at the formaldehyde of quality, also available acetaldehyde is replaced, the consumption of acetaldehyde is identical with the molal quantity of the formaldehyde of quality such as paraformaldehyde, it is that 4000～200000 polyethylene glycol or molecular weight are that 48000 polyvinyl chloride is replaced that ternary nylon such as uses at the molecular weight of quality, and other steps of this step are identical with respective embodiments.Other steps are identical with respective embodiments.
Embodiment 5
In above embodiment 1～4 preparation consolidation liquid step 5, raw materials used mass concentration be 37% formaldehyde replace with equimolar acetaldehyde or use with mass concentration be that the paraformaldehyde of 37% quality such as formaldehyde is replaced, to be 36% hydrochloric acid replace with sulfuric acid or phosphoric acid or oxalic acid mass concentration, promptly 1 mole hydrochloride is replaced with 1/2 mol sulfuric acid or is replaced or 1/2 mole oxalic acid replacement with 1/3 mole of phosphoric acid, and other steps of this step are identical with respective embodiments.Other steps are identical with respective embodiments.
Embodiment 6
In above embodiment 1～5 back flow reaction step 2, reactant is heated to 95～102 ℃ under stirring, reacted 1 hour.Other steps are identical with respective embodiments.
Embodiment 7
In above embodiment 1～5 back flow reaction step 2, reactant is heated to 95～102 ℃ under stirring, reacted 9 hours.Other steps are identical with respective embodiments.
In order to determine optimised process step of the present invention, the inventor has carried out a large amount of laboratory study tests, and various test situation are as follows:
Experiment material: paraformaldehyde, the degree of polymerization are 8～100 low molecular weight polyformaldehyde, analyze purely, and the rich Dihua worker Co., Ltd in Tianjin produces; Manganese acetate, Mn (CH
3COO)
24H
2O, molecular weight 245.09 is analyzed purely, and Chemical Reagent Co., Ltd., Sinopharm Group produces; Cobalt acetate, Co (CH
3COO)
24H
2O, molecular weight 249.08 is analyzed purely, and chemical reagent factory in Xi'an produces; Schweinfurt green, Cu (CH
3COO)
2H
2O, molecular weight 199.65 is analyzed purely, and Chemical Reagent Co., Ltd., Sinopharm Group produces; Hydrochloric acid, HCl, molecular weight 36.46, analyze pure, content of hydrochloric acid＞36%, Xi'an chemical reagent factory.Acetic acid, CH
3COOH, molecular weight 60.05, analyze pure, acetic acid content＞99.5%, Tianjin causes chemical reagent far away Co., Ltd; Citric acid, C
6H
8O
7H
2O, molecular weight 210.14, analyze pure, citric acid content＞99.5%, Xi'an chemical reagent factory; Maleic acid, C
4H
4O
4, molecular weight 116.08, analyze pure, maleic acid content＞99.5%, the imperial chemical reagent of Beijing gold Co., Ltd; Molecular weight is 4000～200000 polyethylene glycol (PEG), analyzes purely, and the Shantou Xilong Chemical Factory, Guangdong produces; Molecular weight is 48000 polyvinyl chloride (PVC), and the good peaking worker Co., Ltd in Ningxia produces; Ternary nylon, Yixing City chemical reagent factory produces.
Laboratory apparatus: resin softening point is measured and is adopted full-automatic bituminous softening-point test device, and model is SYD-2806E, builds mechanical ﹠ electronic equipment corporation, Ltd admittedly by Guangzhou and produces; Measure the molecular resin amount and distribute and adopt gel permeation chromatography, model is GPC-717/1515/2414, produce by U.S. Waters company, 35 ℃ of tests down, splitter is Aquapak A-440 (HR 1.0, and HR 2.0, and HR 3.0), flow rate 1.0mL/ minute of solvents tetrahydrofurane (THF), standard specimen is that molecular weight is 474～205000g/mol monodisperse polystyrene; Sample adjacency pair position is analyzed and is adopted superconduction Fourier numeralization nuclear magnetic resonance spectrometer, and model is Advance 300MHz, is produced by Bruker company; Dynamic viscoelasticity spectrum instrument, model are Q800DMA, are produced by U.S. TA company; Limiting oxygen index determination instrument, model are LFY-606, are produced by Shandong Province's textile research institute; Dynamic viscoelasticity spectrum instrument, model are Q800DMA, are produced by U.S. TA company; Limiting oxygen index determination instrument, model are LFY-606, are produced by Shandong Province's textile research institute.
1, phenolic compound and aldehyde compound proportioning determines
(1) batching
Get totally 8 parts of phenol 94g, get the degree of polymerization respectively and be 8～100 paraformaldehyde 15.78g, 17.36g, 18.94g, 20.52g, 22.10g, 23.68g, 25.26g, 28.42g, get each 8 parts of maleic acid 1.16g, Schweinfurt green 1.40g, ternary nylon 4.70g, place reactor respectively, stir, be that paraformaldehyde, the maleic acid of quality such as phenol and formaldehyde, the mol ratio of Schweinfurt green are 1: 0.50,0.55,0.60,0.65,0.70,0.75,0.80,0.90: 0.010: 0.007, the mass ratio of phenol and ternary nylon is 1: 0.05.
(2) back flow reaction
Reactant is heated to 95～102 ℃ under stirring, isothermal reaction 5 hours.
(3) vacuumize
After reaction finishes, product is put into the vacuum drying oven of vacuum for-0.07MPa, 180 ℃ of vacuumize 4 hours is prepared into toughening agent modified novolac resin.
Prepared toughening agent modified novolac resin adopts the softening point of full-automatic bituminous softening-point test device by GB/T8146-2003 " rosin experimental technique " test phenolic resins; Press the free content determination that divides of GB/T 14074.13-93 and detect free phenol content; Adopt gel permeation chromatography, measure phenolic resins molecular weight and distribution thereof down at 35 ℃, splitter is that (HR 1.0 for Aquapak A-440, HR 2.0, HR 3.0), the flow rate of solvents tetrahydrofurane is 1.0mL/ minute, standard specimen is that molecular weight is 474～205000g/mol monodisperse polystyrene; Adopt the DEPT-135 spectrum, calculate phenolic resins peak (30ppm) the area S of neighbour-neighbour's link
1, adjacent-to phenolic resins peak (35ppm) the area S of link
2With right-to the link phenolic resins peak (40ppm) area S
3, calculate resin adjacency pair position ratio by following formula (1):
Test and result of calculation see Table 1.
(4) preparation as-spun fibre
Toughening agent modified novolac resin is put into the melt spinning device spinning, the concrete grammar of melt spinning is the preparation method that 3650102 the disclosed fiber of United States Patent (USP) forms from the direct drawing-off of molten according to the patent No., being about to the toughening agent modified novolac resin of 100g packs in the melt spinning still of single hole spinnerets with 1.9mm aperture, be warming up to 135 ℃, toughening agent modified novolac resin becomes molten, melt flows out from spinneret orifice, the drawing-off top roll, drafting rate is 915m/ minute, is prepared into as-spun fibre.
(5) preparation consolidation liquid
Water intaking 90g, mass concentration are that 36% hydrochloric acid 50.70g, mass concentration are 37% formaldehyde 81.10g, and the mol ratio of water and hydrochloric acid, formaldehyde is 1: 0.1: 0.2.
(6) curing reaction
As-spun fibre 2g is placed the 100g consolidation liquid, at the uniform velocity be warming up to 100 ℃ in 6 hours, isothermal reaction 2.5 hours.
(7) washing is dry
After reaction finishes, take out fiber, use deionized water rinsing 3～5 times, dry naturally, be prepared into toughening agent modified phenolic fiber.
(8) testing performance index
To TENSILE STRENGTH and the elastic modelling quantity of prepared toughening agent modified phenolic fiber, with limiting oxygen index determination instrument determination limit oxygen index (OI) with dynamic viscoelasticity spectrum instrument mensuration toughening agent modified phenolic fiber.
Test result sees Table 1.
Table 1 aldehyde and phenol mol ratio are to the influence of toughening agent modified phenolic resins and fibre property
By table 1 as seen, the mol ratio of phenolic compound and aldehyde compound is 1: 0.50～0.90, every performance of prepared phenolic resins and the TENSILE STRENGTH of phenolic fibre, elastic modelling quantity and limited oxygen index better performances.It is 1: 0.50～0.90 that the present invention selects the mol ratio of phenolic compound and aldehyde compound, and preferred molar ratio is 1: 0.65～0.90, and optimum mole ratio is 1: 0.70.
2, divalence acetate determines
Get each 4 parts of phenol 94g, paraformaldehyde 22.10g, maleic acid 1.16g, ternary nylon 4.70g, get manganese acetate 1.71g, cobalt acetate 1.74g, Schweinfurt green 1.40g respectively, place reactor respectively, stir, be that paraformaldehyde, the maleic acid of quality such as phenol and formaldehyde, the mol ratio of divalence acetate are 1: 0.70: 0.010: 0.007, the mass ratio of phenol and ternary nylon is 1: 0.05, and other steps are identical with experiment 1, are prepared into toughening agent modified novolac resin.Prepared toughening agent modified novolac resin is tested, and used tester is identical with experiment 1 with method of testing and computing formula.Test and result of calculation see Table 2.
Prepared toughening agent modified novolac resin 1 is made toughening agent modified phenolic fiber according to experiment, it is carried out TENSILE STRENGTH, elastic modelling quantity, limited oxygen index test.
Test result sees Table 2.
Table 2 divalence acetate is to the influence of toughening agent modified phenolic resins and fibre property
By table 2 as seen, adopt cobalt acetate or manganese acetate or Schweinfurt green to make catalyst, every performance of prepared phenolic resins and the TENSILE STRENGTH of phenolic fibre, elastic modelling quantity and limited oxygen index better performances.The present invention selects cobalt acetate or manganese acetate or Schweinfurt green as catalyst, preferred Schweinfurt green or cobalt acetate, optimal selection Schweinfurt green.
3, divalence acetate proportioning determines
Get each 7 parts of phenol 94g, paraformaldehyde 22.10g, maleic acid 1.16g, ternary nylon 4.70g, get Schweinfurt green 1.00g, 1.20g, 1.40g, 1.60g, 2.00g, 3.00g, 4.00g respectively, place reactor respectively, stir, be that paraformaldehyde, the maleic acid of quality such as phenol and formaldehyde, the mol ratio of Schweinfurt green are 1: 0.70: 0.010: 0.005,0.006,0.007,0.008,0.010,0.015,0.020, the mass ratio of phenol and ternary nylon is 1: 0.05.Other steps are identical with experiment 1, are prepared into toughening agent modified novolac resin.Prepared toughening agent modified novolac resin is tested, and used tester is identical with experiment 1 with method of testing and computing formula.Test and result of calculation see Table 3.
Prepared toughening agent modified novolac resin 1 is made toughening agent modified phenolic fiber according to experiment, it is carried out TENSILE STRENGTH, elastic modelling quantity, limited oxygen index test.
Test result sees Table 3.
Table 3 divalence acetate proportioning is to the influence of toughening agent modified phenolic resins and fibre property
By table 3 as seen, the mol ratio of phenol and divalence acetate is 1: 0.005～0.020, every performance of prepared phenolic resins and the TENSILE STRENGTH of phenolic fibre, elastic modelling quantity and limited oxygen index better performances.It is 1: 0.005～0.020 that the present invention selects the mol ratio of phenol and divalence acetate, and preferred molar ratio is 1: 0.005～0.015, and optimum mole ratio is 1: 0.007.
4, organic acid or inorganic acid determines
Get each 5 parts of phenol 94g, paraformaldehyde 22.10g, Schweinfurt green 1.40g, ternary nylon 4.70g, acetic acid 0.60g, hydrochloric acid 0.36g, maleic acid 1.16g, citric acid 2.10g, place reactor respectively, stir, paraformaldehyde, organic acid or the inorganic acid, the Schweinfurt green mol ratio that are quality such as phenol and formaldehyde are 1: 0.70: 0.010: 0.007, and the mass ratio of phenol and ternary nylon is 1: 0.05.Other steps are identical with experiment 1, are prepared into toughening agent modified novolac resin.Used tester is identical with experiment 1 with method of testing and computing formula.Test and result of calculation see Table 4.
Prepared toughening agent modified novolac resin 1 is made toughening agent modified phenolic fiber according to experiment, it is carried out TENSILE STRENGTH, elastic modelling quantity, limited oxygen index test.
Test result sees Table 4.
By table 4 as seen, adopt acetic acid or maleic acid or citric acid or hydrochloric acid as second catalyst, the TENSILE STRENGTH of every performance of prepared phenolic resins and phenolic fibre, elastic modelling quantity and limited oxygen index better performances.The present invention selects acetic acid or hydrochloric acid or maleic acid or citric acid as second catalyst, and preferred maleic acid or hydrochloric acid is as second catalyst, the optimal selection maleic acid.
Table 4 organic acid or inorganic acid are to the influence of toughening agent modified phenolic resins and fibre property
5, determine organic acid or inorganic acid proportioning
Get each 7 parts of phenol 94g, paraformaldehyde 22.10g, Schweinfurt green 1.40g, ternary nylon 4.70g, maleic acid 0.58g, 0.81g, 1.04g, 1.16g, 1.74g, 2.32g, 2.90g, place reactor respectively, stir, be that paraformaldehyde, the maleic acid of quality such as phenol and formaldehyde, the mol ratio of Schweinfurt green are 1: 0.70: 0.005,0.007,0.009,0.010,0.015,0.020,0.025: 0.007, the mass ratio of phenol and ternary nylon is 1: 0.05.Other steps are identical with experiment 1, are prepared into toughening agent modified novolac resin.Used tester is identical with experiment 1 with method of testing and computing formula.Test and result of calculation see Table 5.
Prepared toughening agent modified novolac resin 1 is made toughening agent modified phenolic fiber according to experiment, it is carried out TENSILE STRENGTH, elastic modelling quantity, limited oxygen index test.Test result sees Table 5.
Table 5 organic acid or inorganic acid proportioning are to the influence of toughening agent modified phenolic resins and fibre property
By table 5 as seen, phenol and organic acid or inorganic acid mol ratio are 1: 0.005～0.025, and every performance of prepared phenolic resins and the TENSILE STRENGTH of fiber, elastic modelling quantity and limited oxygen index performance are cut with scissors.It is 1: 0.005～0.025 that the present invention selects phenol and organic acid or inorganic acid mol ratio, and preferred molar ratio is 1: 0.009～0.020, and optimum mole ratio is 1: 0.010.
6, flexibilizer determines
Get phenol 94g, paraformaldehyde 22.10g, maleic acid 1.16g, Schweinfurt green 1.40g, difference taking polyethylene glycol-4000, polyethylene glycol-10000, polyethylene glycol-50000, polyethylene glycol-200000, ternary nylon, each 4.70g of polyvinyl chloride-48000, place reactor, stir, be the formaldehyde of quality such as phenol and paraformaldehyde, maleic acid, the mol ratio of Schweinfurt green is 1: 0.70: 0.010: 0.007, and phenol and polyethylene glycol-4000, polyethylene glycol-10000, polyethylene glycol-50000, polyethylene glycol-200000, ternary nylon, the mass ratio of polyvinyl chloride-48000 is 1: 0.05.Other steps are identical with experiment 1, are prepared into toughening agent modified phenolic resins.Prepared toughening agent modified phenolic resins and toughening agent modified phenolic fiber are tested, and used tester is identical with experiment 1 with method of testing and computing formula.Test and result of calculation see Table 6.
Prepared toughening agent modified phenolic resins 1 is made toughening agent modified phenolic fiber according to experiment, it is carried out TENSILE STRENGTH, elastic modelling quantity, limited oxygen index test.
Test result sees Table 6.
The different flexibilizer of table 6 are to the influence of toughening agent modified phenolic resins and fibre property
By table 6 as seen, adopt polyethylene glycol-4000 or polyethylene glycol-10000 or polyethylene glycol-50000 or polyethylene glycol-200000 or ternary nylon or polyvinyl chloride-48000 as flexibilizer, every performance of prepared phenolic resins and the TENSILE STRENGTH of phenolic fibre, elastic modelling quantity and limited oxygen index better performances.It is that 4000～200000 polyethylene glycol or ternary nylon or molecular weight are that 48000 polyvinyl chloride is as flexibilizer that the present invention selects the dimeric molecule amount, preferred molecular weight be 10000 polyethylene glycol or molecular weight be 200000 polyethylene glycol or ternary nylon as flexibilizer, the best is a ternary nylon.
7, the flexibilizer proportioning determines
Get each 7 parts of phenol 94g, paraformaldehyde 22.11g, maleic acid 1.16g, Schweinfurt green 1.40g, get ternary nylon-20 .94g, 1.88g, 2.82g, 3.76g, 4.70g, 5.64g, 6.58g respectively, place reactor, stir, promptly the mol ratio of the paraformaldehyde of quality such as phenol and formaldehyde, maleic acid, Schweinfurt green is 1: 0.70: 0.010: 0.007.The mass ratio of phenol and ternary nylon is 1: 0.01,0.02,0.03,0.04,0.05,0.06,0.07.Other steps are identical with experiment 1, are prepared into toughening agent modified novolac resin.Prepared toughening agent modified novolac resin is tested, and used tester is identical with experiment 1 with method of testing and computing formula.Test and result of calculation see Table 7.
Prepared toughening agent modified novolac resin 1 is made toughening agent modified phenolic fiber according to experiment, it is carried out TENSILE STRENGTH, elastic modelling quantity, limited oxygen index test.
Test result sees Table 7.
Table 7 flexibilizer proportioning changes the influence of part phenolic resins and fibre property to flexibilizer
By table 7 as seen, the mass ratio of phenol and flexibilizer is 1: 0.01～0.07, every performance of prepared phenolic resins and the TENSILE STRENGTH of phenolic fibre, elastic modelling quantity and limited oxygen index better performances.It is 1: 0.01～0.07 that the present invention selects the mass ratio of phenol and flexibilizer, and the preferred mass ratio is 0.04～0.06, and optimum quality ratio is 1: 0.05.
8, determine the reaction time
Get respectively 9 parts of phenol 94g, paraformaldehyde 22.10g, Schweinfurt green 1.40g, maleic acid 1.16g, ternary nylon 4.70g, place reactor respectively, stir, be that paraformaldehyde, the maleic acid of quality such as phenol and formaldehyde, the mol ratio of Schweinfurt green are 1: 0.70: 0.010: 0.007, phenol is 1: 0.05 mixing with the mass ratio of ternary nylon, be warming up to 100 ℃, isothermal reaction is 1,2,3,4,5,6,7,8,9 hours respectively.Other steps are identical with experiment 1, are prepared into toughening agent modified novolac resin.Used tester is identical with experiment 1 with method of testing and computing formula.Test and result of calculation see Table 8.
Prepared toughening agent modified novolac resin 1 is made toughening agent modified phenolic fiber according to experiment, it is carried out TENSILE STRENGTH, elastic modelling quantity, limited oxygen index test.Test result sees Table 8.
Table 8 reaction time is to the influence of toughening agent modified phenolic resins and fibre property
By table 8 as seen, back flow reaction 1～9 hour, every performance of prepared phenolic resins and the TENSILE STRENGTH of fiber, elastic modelling quantity and limited oxygen index better performances.The present invention selected back flow reaction 1～9 hour, preferred back flow reaction 2～7 hours, best back flow reaction 5 hours.
Claims (3)
1. the preparation method of a toughening agent modified phenolic fiber is characterized in that it comprises the steps:
(1) batching
Take by weighing phenolic compound, aldehyde compound, organic acid or inorganic acid, divalence acetate, flexibilizer, place reactor, stir, the mol ratio of phenolic compound and aldehyde compound, organic acid or inorganic acid, divalence acetate is 1: 0.50～0.90: 0.005～0.025: 0.005～0.020, and the mass ratio of phenolic compound and flexibilizer is 1: 0.01～0.07;
Above-mentioned phenolic compound is phenol or m-cresol; Aldehyde compound be formaldehyde or acetaldehyde or with the paraformaldehyde of quality such as formaldehyde, paraformaldehyde is that the degree of polymerization is 8～100 low molecular weight polyformaldehyde; Divalence acetate is manganese acetate or cobalt acetate or Schweinfurt green; Organic acid is maleic acid or citric acid or acetic acid, and inorganic acid is a hydrochloric acid; Flexibilizer is that molecular weight is that 4000～200000 polyethylene glycol, ternary nylon, molecular weight are any one in 48000 the polyvinyl chloride;
(2) back flow reaction
Reactant is heated to 95～102 ℃ under stirring, reacted 1～9 hour;
(3) vacuumize
After reaction finishes, product is put into the vacuum drying oven of vacuum for-0.07MPa, continue to be heated with stirring to 180 ℃, vacuumize 4 hours is prepared into toughening agent modified novolac resin;
(4) preparation as-spun fibre
The toughening agent modified novolac resin of 100g is packed in the melt spinning still of single hole spinnerets with 1.9mm aperture, be warming up to 135 ℃, toughening agent modified novolac resin becomes molten, melt flows out from spinneret orifice, the drawing-off top roll, drafting rate is 915m/ minute, is prepared into as-spun fibre;
(5) preparation consolidation liquid
Water intaking, acid, aldehyde compound are mixed with consolidation liquid, and water is 1: 0.1: 0.2 with the mol ratio of acid, aldehyde compound;
Above-mentioned aldehyde compound be formaldehyde or acetaldehyde or with the paraformaldehyde of quality such as formaldehyde; Above-mentioned acid is hydrochloric acid or sulfuric acid or oxalic acid or phosphoric acid, promptly uses 1 mole hydrochloride or 1/2 mol sulfuric acid or 1/2 mole of oxalic acid or 1/3 mole of phosphoric acid;
(6) curing reaction
As-spun fibre is placed consolidation liquid, and the quality of as-spun fibre is 2% of a consolidation liquid gross mass, at the uniform velocity is warming up to 100 ℃ in 6 hours, isothermal reaction 2.5 hours;
(7) washing is dry
After reaction finishes, take out fiber, use deionized water rinsing 3～5 times, dry naturally, be prepared into toughening agent modified phenolic fiber.
2. according to the preparation method of the described toughening agent modified phenolic fiber of claim 1, it is characterized in that: in batching step (1), the mol ratio of phenolic compound and aldehyde compound, organic acid or inorganic acid, divalence acetate is 1: 0.65～0.90: 0.009～0.020: 0.005～0.015, and the mass ratio of phenolic compound and flexibilizer is 1: 0.04～0.06; In back flow reaction step (2), reactant is heated to 95～102 ℃ under stirring, reacted 2～7 hours.
3. according to the preparation method of the described toughening agent modified phenolic fiber of claim 1, it is characterized in that: in batching step (1), the mol ratio of phenolic compound and aldehyde compound, organic acid or inorganic acid, divalence acetate is 1: 0.70: 0.010: 0.007, and the mass ratio of phenolic compound and flexibilizer is 1: 0.05; In back flow reaction step (2), reactant is heated to 95～102 ℃ under stirring, reacted 5 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102199265A (en) * | 2011-03-28 | 2011-09-28 | 浙江嘉民塑胶有限公司 | Long carbon chain nylon modified phenolic resin and preparation method thereof |
| CN103046154A (en) * | 2013-01-15 | 2013-04-17 | 中原工学院 | Preparation method of dual-catalytic phenolic aldehyde fibers |
| CN103060941A (en) * | 2013-01-15 | 2013-04-24 | 中原工学院 | Preparation method of high molecular weight phenolic fiber |
| CN104674381A (en) * | 2015-03-16 | 2015-06-03 | 山东莱芜润达新材料有限公司 | High-carbon-yield asphalt-phenolic fiber |
| CN105348731A (en) * | 2015-11-13 | 2016-02-24 | 安徽广源科技发展有限公司 | High-toughness plastic used for high-temperature electric appliances |
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| CN1440989A (en) * | 2003-03-21 | 2003-09-10 | 中国科学院山西煤炭化学研究所 | Synthesis of high-purity phenolic resin preparing superfine fiber |
| CN1440990A (en) * | 2003-03-21 | 2003-09-10 | 中国科学院山西煤炭化学研究所 | Prepn of high-moleculr weight phenolic resin for spinning |
| CN101289767B (en) * | 2008-06-13 | 2013-03-20 | 陕西师范大学 | Method for preparing phenolic resin fiber of high molecular weight |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102199265A (en) * | 2011-03-28 | 2011-09-28 | 浙江嘉民塑胶有限公司 | Long carbon chain nylon modified phenolic resin and preparation method thereof |
| CN102199265B (en) * | 2011-03-28 | 2012-10-10 | 浙江嘉民塑胶有限公司 | Long carbon chain nylon modified phenolic resin and preparation method thereof |
| CN103046154A (en) * | 2013-01-15 | 2013-04-17 | 中原工学院 | Preparation method of dual-catalytic phenolic aldehyde fibers |
| CN103060941A (en) * | 2013-01-15 | 2013-04-24 | 中原工学院 | Preparation method of high molecular weight phenolic fiber |
| CN103060941B (en) * | 2013-01-15 | 2015-10-07 | 中原工学院 | A kind of preparation method of high molecular weight phenolic fiber |
| CN104674381A (en) * | 2015-03-16 | 2015-06-03 | 山东莱芜润达新材料有限公司 | High-carbon-yield asphalt-phenolic fiber |
| CN105348731A (en) * | 2015-11-13 | 2016-02-24 | 安徽广源科技发展有限公司 | High-toughness plastic used for high-temperature electric appliances |
| CN116005490A (en) * | 2022-12-12 | 2023-04-25 | 太尔胶粘剂(广东)有限公司 | High-toughness impregnated film paper and preparation method and application thereof |
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